US6916896B2 - High productivity spandex fiber process and product - Google Patents
High productivity spandex fiber process and product Download PDFInfo
- Publication number
- US6916896B2 US6916896B2 US10/430,060 US43006003A US6916896B2 US 6916896 B2 US6916896 B2 US 6916896B2 US 43006003 A US43006003 A US 43006003A US 6916896 B2 US6916896 B2 US 6916896B2
- Authority
- US
- United States
- Prior art keywords
- glycol
- mdi
- mole percent
- spandex
- polyurethaneurea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/906—Fiber or elastomer prepared from an isocyanate reactant
Definitions
- the present invention relates to a highly soluble polyurethaneurea prepared from: (a) at least one polymeric glycol; (b) a diisocyanate mixture comprising: (i) at least about 78 mole percent 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene (4,4′-MDI); and (ii) at least about 5 mole percent 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene (2,4′-MDI); (c) at least one chain extender; and (d) at least one amine chain terminator.
- the present invention also relates to a method of producing spandex fiber from a high-solids solution of said polyurethaneurea and to the spandex fibers thus formed.
- Spandex is the generic name for manufactured fiber in which the fiber-forming substance is a long-chain synthetic polymer comprised of at least 85% of a segmented polyurethane.
- the present invention herein is discussed in terms of spandex, but should be construed to include all embodiments described in the following disclosure and their equivalents.
- Spandex is typically prepared in two steps. First a low molecular weight difunctional polymer, such as a polymeric glycol, is allowed to react with a diisocyanate to form a mixture of isocyanate-terminated prepolymer and unreacted diisocyanate (“capped glycol”). The capped glycol is then dissolved in a suitable solvent and reacted with a difunctional chain extender and monofunctional chain terminator composition to form a polyurethaneurea polymer solution. Commercial spandex fiber is then formed from the resulting polyurethaneurea solution using conventional dry-spinning or wet-spinning techniques.
- a low molecular weight difunctional polymer such as a polymeric glycol
- spandex comprises so-called “hard” segments derived from the reaction between an isocyanate group on the capped glycol and the chain extender.
- Spandex also comprises “soft” segments derived primarily from the polymeric glycol. It is believed that the desirable elastomeric properties of spandex are due, in part, to this segmented structure.
- chain extender like ethylenediamine, may react with isocyanate groups from the capped glycol, in certain cases only one end of the chain extender may react.
- the result is a polymer having a chain extender with a primary amine at one end.
- the number of these “chain extender ends” (CE), expressed as the concentration of ends in milliequivalents per kilogram of polymer, can be determined by measuring the concentration of primary amine in the polymer. Primary amine content can be assayed using conventional techniques.
- the number of chain extender ends can be controlled by several means, such as by varying the stoichiometry of chain extender to capped glycol.
- the number of chain extender ends can be controlled using a chain terminator, such as diethylamine (DEA).
- DEA diethylamine
- a chain terminator reacts with the capped glycol, in the same manner as a chain extender, but does not have a second reactive group. The result is a polymer with a chain terminator end rather than a chain extender end.
- the combination of a desired number of polymer ends with a desired proportion of those being chain extender ends is an aspect of the present invention and can be described in terms of polymer properties normally measured in the art.
- the total number of polymer ends is directly proportional to the IV.
- the number of chain extender ends is related to the quantity of primary amine in the polymer.
- describing aspects of the present invention in terms of desirable IV and amount of primary amine is the equivalent to describing those aspects in terms of the desirable number of polymer ends and chain extender ends, respectively. The reader is directed to the Examples for further details.
- Spandex fiber can be formed from the polyurethaneurea through fiber spinning processes such as dry spinning.
- dry spinning a polymer solution comprising a polymer and solvent is metered through spinneret orifices into a spin chamber to form a filament or filaments. Gas is passed through the chamber to evaporate the solvent to solidify the filament(s). Multiple filaments can then be coalesced into a spandex yarn.
- Solvents used in polymer solutions should provide a homogeneous solution containing little or no gels.
- Solvents particularly suitable for dry spinning include N,N-dimethylacetamide (DMAc), N-methylpyrrolidinone (NMP), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Because of safety and cost concerns DMAc is preferred and, indeed, used almost exclusively in the industry.
- the productivity of dry spinning is typically described in terms of grams of yarn per spin chamber per hour and is related to winding speed, yarn and filament deniers and to the number of yams per spin chamber. Such parameters, however, are limited by the volume and solvent used in the polymer solution and the rate of solvent evaporation through the surface of each filament. The rate of evaporation, in turn, is related to the filament denier and to the number of filaments within the spin chamber. For example, an increase in filament denier, while maintaining the total yarn denier, means a decrease in overall filament surface area and a slower rate of solvent evaporation. Winding speed must be reduced in such cases to allow sufficient time for the solvent to evaporate within the spin chamber.
- the more filaments in a spin chamber the larger the volume of gas and solvent vapor that must be handled. High volumes of gas induce turbulence which reduces fiber uniformity, process continuity, and productivity. Further, the volume of solvent used and its rate of evaporation from the filaments may affect the physical properties of the spandex fiber such as tenacity.
- spandex fiber must meet certain properties recognized in the industry. While small markets may exist for spandex that does not meet these properties, such niche applications are quite limited and it is the purpose of the present invention to have a broad application in the spandex industry. These properties are appreciated by those skilled in the art and include, for example for spandex at 40 denier: IV greater than 1.1 dl/g; Tenacity at least 40 g; Load Power (1TP2) less than 7 g; Unload Power (5TM2) at least 0.9 g; and a coefficient of denier variation (CDV) less than 15.
- the present invention relates to a polyurethaneurea for use in a high-solids content polymer solution for the production of spandex fiber.
- Another aspect of the invention is an improved method for producing spandex fiber from a high-solids content polyurethaneurea polymer solution.
- Yet another aspect of the invention is a commercially acceptable spandex fiber produced by dry spinning a high-solids content polyurethaneurea polymer solution.
- the polyurethaneurea of the present invention prior to spinning has an IV between about 0.65 and about 0.90 dl/g, a primary amine content between about 25 and about 55 milliequivalents NH 2 per kilogram of polymer solids (meq/Kg), and is prepared from: at least one polymeric glycol; a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI; at least one chain extender; and at least one amine chain terminator.
- the high-solids content polymer solution of the present invention comprises a DMAc solution that is greater than 38 weight percent of said polyurethaneurea.
- spandex fiber can be improved dramatically by first preparing a highly soluble polyurethaneurea having a desirable IV (i.e., total ends) and a desirable primary amine content (i.e., chain extender ends), and then preparing a polymer solution comprising said polyurethaneurea in greater than 38 weight percent.
- a desirable IV i.e., total ends
- a desirable primary amine content i.e., chain extender ends
- polyurethane urea of the present invention is prepared from:
- polyether glycols suitable for use in the present invention have number average molecular weights of from about 1500 to about 4000, preferably from about 1600 to about 2500, and more preferably from about 1800 to about 2000.
- Useful polyether glycols include, but are not limited to, polyethyleneether glycol, polytrimethyleneether glycol, polytetramethyleneether glycol, polytetramethylene-co-2-methyl-tetramethyleneether glycol, polytetramethylene-co-ethylene glycol, and mixtures thereof. Most preferred is polytetramethylene glycol such as TERATHANE® 1800 (available from Dupont Co.).
- polyester glycols include, but are not limited to, copoly(ethylene-butylene adipate) diol, poly(2,2-dimethylpropylene dodecanoate) diol, hydroxy-terminated reaction products of diols such as ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol, 2,2-dimethyl-1,3-propane diol, 3-methyl-1,5-pentane diol, and mixtures thereof.
- a mixture of diisocyanates is used to make the polyurethaneurea of the present invention.
- One component of the diisocyanate mixture is 4,4′-MDI present in at least about 78 mole percent, preferably from about 80 to about 95 mole percent, most preferably about 83 to about 91 mole percent.
- a second component of the diisocyanate mixture is 2,4′-MDI present in at least about 5 mole percent, preferably from about 7 to about 20 mole percent, more preferably from about 9 to about 17 mole percent. It is preferred that there be less than 1 mole percent 2,2′-MDI in the mixture of diisocyanates.
- the diisocyanate mixture can be added all at once or in two or more steps and in any order. If desired, dibutyltin dilaurate, stannous octoate, mineral acids, tertiary amines such as triethylamine, N,N′-dimethylpiperazine, and the like, and other known catalysts can be used to assists in the capping step.
- the capped glycol is then added to a suitable solvent such as DMAc, DMF, DMSO, N-methylpyrrolidinone (NMP), and the like, including mixtures. DMAc is preferred.
- a single chain extender or a mixture of chain extenders may be used to prepare the polyurethaneurea of the present invention from the capped glycol. If a single chain extender is used, it is preferably ethylenediamine (EDA). If a mixture of chain extenders is used, the mixture should comprise at least about 90 mole percent EDA as a primary chain extender and further include one or more secondary chain extenders.
- EDA ethylenediamine
- secondary chain extenders examples include 2-methyl-1,5-pentanediamine (MPMD commercially available as DYTEK® A, available from DuPont), 1,2-propanediamine (PDA), 1,3-butanediamine, 1,4-butanediamine, 1,3-diamino-2,2-dimethylbutane, 1,6-hexanediamine, 1,3-propanediamine, N-methylaminobis(3-propylamine) 2-methyl-1,5-pentanediamine, 1,5-diaminopentane, 1,4-cyclohexanediamine, 1,3-diamino-4-methylcyclohexane, 1,3-cyclohexanediamine, 1,1′-methylene-bis(4,4′-diaminohexane), 1,3-diaminopentane, piperazine, cyclohexylene-1,3-diamine (hydrogenated m-phenylene diamine), isophorone diamine, 1,4-di
- Suitable chain terminators include secondary amines, for example diethylamine (DEA), diisopropylamine, piperidine, dibutylamine, and mixtures thereof. DEA is preferred.
- the chain extender and chain terminators can be added all at once or in two or more steps, preferably all at once. It is preferred that the chain extender(s) and chain terminator(s) be dissolved in a suitable solvent, as defined above. DMAc is the preferred solvent.
- an effective amount of a variety of additives can also be used in the spandex of the invention, provided they do not detract from the beneficial aspects of the invention.
- examples include delustrants such as titanium dioxide and stabilizers such as hydrotalcite, a mixture of huntite and hydromagnesite, barium sulfate, hindered phenols, and zinc oxide, dyes and dye enhancers, antimicrobials, antitack agents, silicone oil, hindered amine light stabilizers, UV screeners, and the like.
- the polymer solution which is dry spun into spandex should have a percent solids content greater than 38 and less than 50 weight percent, preferably between about 40 and about 48 weight percent, more preferably about 45 weight percent.
- polymer solution may be stored after initial preparation for periods of 2 to 48 hours prior to spinning, typically at temperatures below 50° C. During this time, the viscosity should not increase excessively to minimize negative impact on spinning performance and yarn properties.
- the 40° C. Falling ball viscosity of the polymers of this invention therefore, increase less than 2000 poises, preferably less than 1500 poises, more preferably less than 1000 poises, when stored at 40° C. for 24 hours.
- pre-spun IV the intrinsic viscosity of the polyurethaneurea, prior to spinning
- the pre-spun IV should be between about 0.65 and about 0.90 dl/g, preferably between about 0.70 and about 0.80, and most preferably about 0.75.
- the amount of chain extender ends in the polyurethaneurea solution is about 25 to about 55 meq/Kg, preferably about 35 to about 45, more preferably about 40.
- the productivity of commercial spandex production can be increased dramatically while simultaneously using less solvent, less gas and less energy. Additionally, the product is more consistent, as measured by coefficient of denier variation, and generates less waste.
- the polyurethaneurea polymers in the examples were prepared according to the following general method. A stoichiometric excess of the diisocyanate mixture was mixed with a polymeric glycol and heated to approximately 90° C. for 2 hours. The resulting capped glycol mixture contained isocyanate terminated polymeric glycol and residual unreacted diisocyanate. The reaction was allowed to continue until the measured weight percent isocyanate (% NCO) was in close agreement with theoretical values based on reaction of all glycol hydroxyl groups with isocyanate. The resulting capped glycol was then completely dissolved in DMAc at about 45° C. under high shear.
- the capped glycol solution was contacted, under high shear, with a DMAc solution containing the appropriate chain extender(s) and chain terminator(s).
- the resulting polymer solution was analyzed for weight percent solids, primary amine content (chain extender ends), pre-spun intrinsic viscosity, and 40° C. Falling ball viscosity.
- An additive solution was added to provide the final fiber with 1.5 weight percent CYANOX® 1790 (Cytec Industries), 0.5 weight percent METHACROL® 2462 (Dupont Co.), and 0.6 weight percent polydimethylsiloxane silicone oil.
- the polymer solution was then dry spun from DMAc into a column into which a stream of heated nitrogen was introduced. The resulting spandex filaments were coalesced, a spin finish was applied, and the fiber was wound onto a package.
- the diisocyanate mixtures used in the examples were prepared by mixing ISONATE® MDR (Dow Chemical Co.) and MONDUR® ML (Bayer AG) in appropriate proportions to obtain the desired levels of 2,4′-MDI.
- ISONATE® MDR is 4,4′-MDI containing a small amount of 2,4′-MDI (approx. 1.9%).
- MONDUR® ML is a mixture of 4,4′-MDI (approx. 44.9%), 2,4′-MDI (approx. 53.2%) and 2,2′-MDI (approx. 2.2%).
- the polyether glycol used in the examples was TERATHANE® 1800 (Dupont) a polytetramethyleneether glycol having a number average molecular weight of 1800.
- the chain extender was either ethylene diamine or a mixture of ethylenediamine (EDA) and 2-methyl-1,5-pentanediamine (DYTEK®A, available from Dupont).
- Intrinsic viscosity (IV) of the polyurethaneurea was determined by comparing the viscosity of a dilute solution of the polymer in DMAc to that of DMAc itself at 25° C. (“relative viscosity” method) in a standard Cannon-Fenske viscometer tube according to ASTM D2515 and is reported as dl/g.
- the number of chain extender ends was determined by dissolving the polymer in DMAc followed by titration for primary amine content with methanesulfonic acid using bromophenol blue as the indicator.
- CDV coefficient of denier variation
- Percent isocyanate (% NCO) of the capped glycols was determined according to the method of S. Siggia, “Quantitative Organic Analysis via Functional Group”, 3rd Edition, Wiley & Sons, New York, pages 559-561 (1963).
- the strength and elastic properties of the spandex were measured in accordance with the general method of ASTM D 2731-72. Three filaments, a 2-inch (5-cm) gauge length and zero-to-300% elongation cycles were used for each of the measurements “as-is” from the windup, that is, without scouring or other treatment. The samples were cycled five times at a constant elongation rate of 50 cm per minute and then held at 300% extension for 30 seconds after the fifth extension. Load power, the stress on spandex during initial extension, was measured on the first cycle at 200% extension and is reported in the Tables in grams and designated “LP”. Unload power, the stress at an extension of 200% on the fifth unload cycle, is also reported in grams; it is designated as “UP”.
- Polyurethaneurea solution viscosity was determined in accordance with the general method of ASTM D1343-69 with a Model DV-8 Falling Ball Viscometer (Duratech Corp., Waynesboro, Va.), operated at 40° C. and is reported in poises. The highest solution viscosity that could be measured using this instrument was 35,000 poises.
- a polyurethaneurea polymer typically used to make spandex was prepared using TERATHANE® 1800 and ISONATE® MDR with a capping ratio of 1:1.69.
- the capped glycol had a % NCO of 2.6% and was diluted with DMAc to give a 45 percent solids solution.
- This solution was then contacted with a DMAc solution containing: a chain extending mixture of EDA and DYTEK® A (90/10 mole ratio); and diethylamine as a chain terminator, in proportions such that the resulting polymer solution had an intrinsic viscosity of 0.95, an initial solution viscosity of 2600 poises and was 34.8 percent solids with the number of chain extender ends measured to be 15 meq/kg of polymer solids.
- a 40 denier, 3 filament spandex yarn was spun from polymer solution at 950 yards per minute (ypm). Intrinsic viscosity of the spun yarn was 1.16.
- a polyurethaneurea polymer of this invention was prepared using a diisocyanate mixture containing 82% ISONATE® MDR and 18% MONDUR® ML.
- the capped glycol was prepared using TERATHANE® 1800 with a capping ratio of 1:1.69.
- the capped glycol was diluted to 55% solids with DMAc and reacted with a mixture of ethylene diamine and diethylamine in DMAc in proportions such that resulting polymer solution had an intrinsic viscosity of 0.75, and an initial solution viscosity of 3300 poise and was 45 percent solids with the number of chain extender ends measured to be 40 meq/kg of polymer solids.
- a 40 denier, 3 filament spandex yarn was spun from polymer solution at 950 yards per minute (ypm). Intrinsic viscosity of the spun yarn was 1.34.
- a polyurethaneurea polymer was prepared using a diisocyanate mixture containing 82% ISONATE ® MDR and 18% MONDUR® ML.
- the capped glycol was prepared using TERATHANE® 1800 with a capping ratio of 1:1.69.
- the capped glycol was diluted to 55% solids with DMAc and reacted with a mixture of ethylene diamine and diethylamine in DMAc in proportions such that resulting polymer solution had an intrinsic viscosity of 0.75, an initial solution viscosity of 3300 poise and was 45 percent solids with the number of chain extender ends measured to be 15 meq/kg of polymer solids.
- a 40 denier, 4 filament spandex yarn was spun from polymer solution at 950 yards per minute (ypm). Intrinsic viscosity of the spun yarn was 1.02.
- a polyurethaneurea polymer was prepared using a diisocyanate mixture containing 82% ISONATE® MDR and 18% MONDUR® ML.
- the capped glycol was prepared using TERATHANE® 1800 with a capping ratio of 1:1.69.
- the capped glycol was diluted to 55% solids with DMAc and reacted with a mixture of ethylene diamine and diethylamine in DMAc in proportions such that resulting polymer solution had an intrinsic viscosity of 0.75, an initial solution viscosity of 3300 poise and was 45 percent solids with the number of chain extender ends measured to be 65 meq/kg of polymer solids.
- a 40 denier, 3 filament spandex yarn was spun from polymer solution at 950 yards per minute (ypm). Intrinsic viscosity of the spun yarn was 1.05.
- a polyurethaneurea polymer was prepared using a diisocyanate mixture containing 82% ISONATE® MDR and 18% MONDUR® ML.
- the capped glycol was prepared using TERATHANE® 1800 with a capping ratio of 1:1.69.
- the capped glycol was diluted to 55% solids with DMAc and reacted with a mixture of ethylene diamine and diethylamine in DMAc in proportions such that resulting polymer solution had an intrinsic viscosity (calculated) of approximately 0.95 (total ends approx. 55), with the number of chain extender ends measured to be 15 meq/kg of polymer solids.
- a 45% solids polymer solution could not be spun into fiber due to the high viscosity and gelling.
- a polyurethaneurea polymer typically used to make spandex was prepared using TERATHANE® 1800 and ISONATE® MDR with a capping ratio of 1.69.
- the capped glycol had a % NCO of 2.6% and was diluted with DMAc to give a 55 percent solids solution of the capped glycol.
- This solution was then contacted with a DMAc solution containing: ethylenediamine chain extender; and diethylamine as a chain terminator, in proportions such that the resulting polymer solution had 45 percent solids with the number of chain extender ends measured to be 40 meq/kg of polymer solids.
- the solution was highly unstable.
- the 40° C. falling ball viscosity increased over 10,000 poise in one hour. The intrinsic viscosity could not be measured and the polymer could not be spun.
- Example 1 shows that merely adjusting the chain extender ends to the desirable level, without also controlling the diisocyanate balance, does not provide a high-solids polymer solution that can be used to prepare spandex.
- Example 2 present invention
- Example 5 shows that having the desirable diisocyanate balance, but without the proper pre-spun IV and without the proper number of chain extender ends, does result in a high viscosity polymer solution that cannot be spun into spandex
- Example 2 presents invention
- Examples 3 and 4 shows that the combination of a proper diisocyanate balance, pre-spun IV and chain extender ends, provides a high-solids polymer solution that can be used to prepare commercially acceptable spandex, as defined in the Background Section of this application.
- Examples 3 and 4 show that without the proper balance of chain extender ends and fiber IV, high-solids polymer solutions can be stable in terms of viscosity, and can be spun, but the spandex fiber will not be commercially acceptable, e.g., a fiber IV of less than 1.1 dl/gm.
- the polyurethaneurea polymer of Example 1 was used to make a 40 denier, two filament spandex yarn and was spun from polymer solution at 672 ypd.
- the fiber properties are reported in Table 2.
- the polyurethaneurea polymer of Example 2 was used to make a 40 denier, two filament spandex yarn and was spun from polymer solution at 672 ypd.
- the fiber properties are reported in Table 2.
- the polyurethaneurea polymer of Example 2 was used to make a 40 denier, two filament spandex yarn and was spun from polymer solution at 807 ypd.
- the fiber properties are reported in Table 2.
- Table 2 demonstrates that the present invention (Examples 8 and 9) provides high-solids polymer solutions that can be used to prepare commercially spandex with even greater consistency (lower CDV) than with prior art systems (Example 7).
- Example 9 further illustrates that using the present invention spandex can be prepared at higher winding speeds, thus greater productivity, than using prior art systems. Note that commercially acceptable spandex was prepared at 807 ypm using the present invention (Example 9) whereas spandex of prior art Example 7 was spun at 672 ypm without achieving commercially acceptable properties (CDV>15). The prior art process of Example 7 would have to be operated at still lower speeds to achieve acceptable spandex properties.
Abstract
Description
-
- (a) at least one polymeric glycol selected from the group consisting of polyether glycols and polyester glycols;
- (b) a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI;
- (c) at least one chain extender; and
- (d) at least one amine chain terminator;
wherein the mole ratio of (a) to (b), known as the “capping ratio,” is between about 1:1.5 and about 1:2, preferably between about 1:1.6 and about 1:1.8, more preferably between about 1:1.65 and about 1:1.75; wherein further, the at least one chain extender (c) and the at least one amine chain terminator (d) are present in amounts such that the polyurethaneurea, prior to spinning, has an IV less than 0.9 with a primary amine content of between about 25 and about 55 meq/Kg, preferably between about 25 and about 45 meq/Kg, and most preferably about 40 meq/Kg.
% SET=100(Lf−Lo)/Lo
wherein Lo and Lf are the filament (yam) length, when held straight without tension, before and after the five elongation/relaxation cycles, respectively.
TABLE 1 | ||
Example |
1 | 2 | 3 | 4 | 5 | 6 | ||
% 2,4′-MDI | 1.9 | 11.1 | 11.1 | 11.1 | 11.1 | 1.9 |
C.R. | 1.69 | 1.69 | 1.69 | 1.69 | 1.69 | 1.69 |
% Solids | 34.8 | 45 | 45 | 45 | 45 | 45 |
Pre-spun IV | 0.95 | 0.75 | 0.75 | 0.75 | 0.95 Calculated | Not measurable |
CE | 15 | 40 | 15 | 65 | 15 | 40 |
Solution Viscosity | 2600 | 3200 | 3200 | 3200 | Not measurable | Not measurable |
(as made) | ||||||
Fiber IV | 1.16 | 1.34 | 1.02 | 1.05 | Not measurable | Not measurable |
Tenacity | 41.6 | 43.5 | 41.0 | 41.8 | — | — |
LP | 6.9 | 5.4 | 4.8 | 5.7 | — | — |
UP | 1.14 | 1.11 | 1.01 | 1.10 | — | — |
CDV | 17.8 | 10.3 | 16.1 | 10.3 | — | — |
Eb | 476 | 468 | 494 | 472 | — | — |
TABLE 2 | ||
Example |
7 | 8 | 9 | ||
% 2,4′-MDI | 1.9 | 11.1 | 11.1 | ||
C.R. | 1.69 | 1.69 | 1.69 | ||
% Solids | 34.8 | 45 | 45 | ||
Pre-spun IV | 0.95 | 0.75 | 0.75 | ||
CE | 15 | 40 | 40 | ||
Solution Viscosity | 2600 | 3200 | 3200 | ||
(as made) | |||||
Spin rate (ypm) | 672 | 672 | 807 | ||
Fiber IV | 1.4 | 1.6 | 1.43 | ||
Tenacity | 54.6 | 41.6 | 45.4 | ||
LP | 5.27 | 4.10 | 4.32 | ||
UP | 1.15 | 1.00 | 1.01 | ||
CDV | 21 | 9.5 | 9.8 | ||
Eb | 546 | 556 | 513 | ||
Claims (26)
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/430,060 US6916896B2 (en) | 2003-05-05 | 2003-05-05 | High productivity spandex fiber process and product |
AT04718099T ATE486897T1 (en) | 2003-05-05 | 2004-03-05 | HIGHLY PRODUCTIVE SPANDEX FIBER MANUFACTURING PROCESS AND PRODUCT |
EP04718099A EP1622958B1 (en) | 2003-05-05 | 2004-03-05 | High productivity spandex fiber process and product |
JP2006509189A JP4764335B2 (en) | 2003-05-05 | 2004-03-05 | High productivity spandex fiber processes and products |
DE602004029882T DE602004029882D1 (en) | 2003-05-05 | 2004-03-05 | HIGHLY PRODUCTIVE SPANDEXFIBER MANUFACTURING PROCESS AND PRODUCT |
BRPI0409052-7B1A BRPI0409052B1 (en) | 2003-05-05 | 2004-03-05 | polyurethane urea production method, urea polyurethane polymer, spandex and spandex fiber production method |
PCT/US2004/006838 WO2004099282A1 (en) | 2003-05-05 | 2004-03-05 | High productivity spandex fiber process and product |
CN200810003050XA CN101195935B (en) | 2003-05-05 | 2004-03-05 | High productivity spandex fiber process and product |
ES04718099T ES2353758T3 (en) | 2003-05-05 | 2004-03-05 | PROCESS FOR OBTAINING FIBER ESPANDEX HIGH PRODUCTIVITY AND PRODUCT OBTAINED. |
CNB2004800120347A CN100379784C (en) | 2003-05-05 | 2004-03-05 | High productivity spandex fiber process and product |
US10/904,317 US7838617B2 (en) | 2003-05-05 | 2004-11-03 | Dyeable spandex |
KR1020057021027A KR101092088B1 (en) | 2003-05-05 | 2005-11-04 | High Productivity Spandex Fiber Process and Products |
HK08112045.2A HK1120296A1 (en) | 2003-05-05 | 2008-11-03 | High productivity spandex fiber process and product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/430,060 US6916896B2 (en) | 2003-05-05 | 2003-05-05 | High productivity spandex fiber process and product |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/904,317 Continuation-In-Part US7838617B2 (en) | 2003-05-05 | 2004-11-03 | Dyeable spandex |
Publications (2)
Publication Number | Publication Date |
---|---|
US20040225101A1 US20040225101A1 (en) | 2004-11-11 |
US6916896B2 true US6916896B2 (en) | 2005-07-12 |
Family
ID=33416170
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/430,060 Expired - Lifetime US6916896B2 (en) | 2003-05-05 | 2003-05-05 | High productivity spandex fiber process and product |
Country Status (11)
Country | Link |
---|---|
US (1) | US6916896B2 (en) |
EP (1) | EP1622958B1 (en) |
JP (1) | JP4764335B2 (en) |
KR (1) | KR101092088B1 (en) |
CN (2) | CN100379784C (en) |
AT (1) | ATE486897T1 (en) |
BR (1) | BRPI0409052B1 (en) |
DE (1) | DE602004029882D1 (en) |
ES (1) | ES2353758T3 (en) |
HK (1) | HK1120296A1 (en) |
WO (1) | WO2004099282A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050165200A1 (en) * | 2003-05-05 | 2005-07-28 | Invista North America S.A.R.L. | Dyeable spandex |
US20060270821A1 (en) * | 2005-05-09 | 2006-11-30 | Palmer Charles F Jr | Spandex compositions for high speed spinning |
CN104153037A (en) * | 2014-08-13 | 2014-11-19 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber with moisture absorption and moisture liberation performance |
CN106884332A (en) * | 2017-03-27 | 2017-06-23 | 浙江鸿辰新材料科技有限公司 | A kind of elastic polyurethane silk fiber and preparation method thereof |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1879937A1 (en) * | 2005-05-09 | 2008-01-23 | INVISTA Technologies S.à.r.l. | Spandex from poly (tetramethylene-co-ethyleneether) glycols having high ethyleneether content |
EP1951782A1 (en) * | 2005-11-22 | 2008-08-06 | INVISTA Technologies S.à.r.l. | Spandex from high molecular weight poly (tetramethylene-co-ethyleneether) glycols |
US20070117949A1 (en) * | 2005-11-22 | 2007-05-24 | Palmer Charles F Jr | Spandex from poly(tetramethylene-co-ethyleneether) glycols having low ethyleneether content |
BRPI0620536A2 (en) * | 2005-11-22 | 2011-11-16 | Invista Tech Sarl | polyurethane, spandex, polyurethane, fabric, textile, article and spandex preparation process |
JP5412715B2 (en) * | 2006-07-12 | 2014-02-12 | 三菱化学株式会社 | Method for producing polyurethane and use of polyurethane obtained therefrom |
AU2008200020B2 (en) * | 2007-01-29 | 2013-07-11 | Bayer Intellectual Property Gmbh | Polyurethanes cured with amines and their preparation |
KR100942359B1 (en) * | 2007-11-06 | 2010-02-12 | 주식회사 효성 | Method for preparing polyurethaneurea elastic fiber with improved heat settability |
WO2009118112A2 (en) * | 2008-03-28 | 2009-10-01 | Bayer Materialscience Ag | 2,2'-mdi-based isocyanate mixtures and the production and use thereof |
CN102899740B (en) * | 2012-11-09 | 2014-05-21 | 浙江华峰氨纶股份有限公司 | Method for preparing low-temperature finalizing polyurethane elastic fiber |
WO2014210378A2 (en) * | 2013-06-28 | 2014-12-31 | Invista Technologies S.A.R.L. | Polyurethaneurea fiber including glycol blend |
WO2015088060A1 (en) * | 2013-12-10 | 2015-06-18 | 주식회사 효성 | Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor |
WO2015088059A1 (en) * | 2013-12-10 | 2015-06-18 | 주식회사 효성 | Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor |
CN103710786B (en) * | 2013-12-18 | 2015-08-12 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the polyurethane stock solution for high speed spinning |
WO2017122879A1 (en) * | 2016-01-15 | 2017-07-20 | (주)효성 | Spandex having improved unwinding properties and enhanced adhesive properties with hot melt adhesive and method for preparing same |
WO2019139217A1 (en) * | 2018-01-11 | 2019-07-18 | 효성 티앤씨 주식회사 | Polyurethaneurea elastic yarn having good toughness and preparation method therefor |
KR20200024054A (en) * | 2018-08-27 | 2020-03-06 | 효성티앤씨 주식회사 | Elastic fiber having improved dying property and manufacturing method thereof |
KR20200024053A (en) * | 2018-08-27 | 2020-03-06 | 효성티앤씨 주식회사 | Elastic fiber having improved dying property |
WO2021146237A1 (en) | 2020-01-17 | 2021-07-22 | Carbon, Inc. | Chemical recycling of additively manufactured objects |
EP4118261A1 (en) * | 2020-03-11 | 2023-01-18 | The LYCRA Company UK Limited | Elastic fiber, composite yarns and fabrics with anti-slippage performance |
CN112899809A (en) * | 2021-02-25 | 2021-06-04 | 汪宜春 | Production process of heat-resistant high-elongation spandex fiber |
WO2023220760A2 (en) * | 2022-05-13 | 2023-11-16 | The Lycra Company Llc | Spandex fibers with improved low-temperature heat settability |
Citations (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3184426A (en) | 1959-04-17 | 1965-05-18 | Bayer Ag | Polyurethane elastic fibers and a method of producing the same |
GB1102819A (en) | 1966-02-01 | 1968-02-14 | Du Pont | Segmented polyurethanes and process therefor |
US3475377A (en) | 1964-12-08 | 1969-10-28 | Bayer Ag | Spandex fibers based on segmented polyurethanes chain extended with two different chain extenders |
US3557044A (en) | 1962-06-07 | 1971-01-19 | Du Pont | Process for making spandex polymers |
US3631138A (en) | 1967-02-17 | 1971-12-28 | Timothy Victor Peters | Solution stable urethane polymer compositions and products therefrom |
US3669934A (en) * | 1964-05-26 | 1972-06-13 | Celanese Corp | Improved elastomeric fibers |
US4973647A (en) | 1989-05-31 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Fiber from polyether-based spandex |
US5000899A (en) | 1988-05-26 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Spandex fiber with copolymer soft segment |
US5032664A (en) | 1989-10-03 | 1991-07-16 | Bayer Aktiengesellschaft | Process for the production of segmented polyurethane urea elastomer solutions and filaments and films thereof |
US5061426A (en) * | 1989-10-03 | 1991-10-29 | Bayer Aktiengesellschaft | Process for producing elastane fibers of high elasticity and strength |
JPH0782608A (en) | 1993-09-10 | 1995-03-28 | Asahi Chem Ind Co Ltd | Prodution of high-tenacity eleasic yarn |
JPH0820625A (en) | 1994-07-07 | 1996-01-23 | Mitsui Toatsu Chem Inc | Production of polyurethane urea solution |
JPH08176268A (en) | 1994-12-26 | 1996-07-09 | Mitsui Toatsu Chem Inc | Production of polyurethaneurea molding |
US5539037A (en) | 1993-09-30 | 1996-07-23 | E. I. Du Pont De Nemours And Company | Spandex containing certain alkali metal salts |
US5644015A (en) | 1996-07-24 | 1997-07-01 | Hyosung T & C Co., Ltd. | Process of manufacturing improved polyurethane fiber polymer |
US5723563A (en) | 1996-10-11 | 1998-03-03 | Arco Chemical Technology, L.P. | Spandex elastomers |
US5843357A (en) | 1996-10-11 | 1998-12-01 | Arco Chemical Technology, L.P. | Spandex elastomers |
US5879799A (en) | 1995-06-23 | 1999-03-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Elastic polyurethane fibers and process for production thereof |
US5948875A (en) | 1998-03-26 | 1999-09-07 | E. I. Du Pont De Nemours And Company | Polyurethaneureas and spandex made therefrom |
US5981686A (en) | 1998-03-26 | 1999-11-09 | E. I. Du Pont De Nemours And Company | Spandex made with 1,3-diaminopentane |
US6403682B1 (en) | 2001-06-28 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Spandex containing quaternary amine additives |
US6472494B2 (en) | 2000-04-26 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Spandex with high heat-set efficiency |
WO2002086208A1 (en) | 2001-04-19 | 2002-10-31 | Kolon Industries, Inc | A polyurethane type elastic fiber, and a process of preparing for the same |
US20020161137A1 (en) * | 2001-04-30 | 2002-10-31 | Wilkinson W. Kenneth | Melt spun thermoplastic polyurethanes useful as textile fibers |
US20020193550A1 (en) | 1999-12-03 | 2002-12-19 | Hiroshi Nishikawa | Spandex having low set at low temperatures |
US6624281B1 (en) * | 2002-05-30 | 2003-09-23 | Bayer Corporation | Polyurethane/ureas useful for the production of spandex and a process for their production |
US6637181B1 (en) * | 1998-06-02 | 2003-10-28 | Bayer Aktiengesellschaft | Elastane threads and method for the production thereof |
US20030224683A1 (en) * | 2002-05-30 | 2003-12-04 | Lawrey Bruce D. | Polyurethane/ureas useful for the production of spandex and a process for their production |
US20030225242A1 (en) * | 2002-05-30 | 2003-12-04 | Lawrey Bruce D. | Prepolymer catalysts suitable for preparing spandex fibers |
US6692828B2 (en) | 2002-04-29 | 2004-02-17 | Hyosung Corporation | High chlorine and heat resistant spandex fiber and manufacturing method thereof |
US6720403B1 (en) * | 2002-11-01 | 2004-04-13 | E.I. Dupont De Nemours And Co. | Polyurethaneurea and spandex comprising same |
US6737497B2 (en) * | 2002-05-30 | 2004-05-18 | Bayer Polymers Llc | Polyurethane/ureas useful for the production of spandex and a process for their production |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100528640B1 (en) * | 1996-10-11 | 2005-11-16 | 아르코 케미컬 테크날러쥐. 엘.피. | Improved spandex elastomer |
-
2003
- 2003-05-05 US US10/430,060 patent/US6916896B2/en not_active Expired - Lifetime
-
2004
- 2004-03-05 AT AT04718099T patent/ATE486897T1/en not_active IP Right Cessation
- 2004-03-05 WO PCT/US2004/006838 patent/WO2004099282A1/en active Application Filing
- 2004-03-05 BR BRPI0409052-7B1A patent/BRPI0409052B1/en not_active IP Right Cessation
- 2004-03-05 ES ES04718099T patent/ES2353758T3/en not_active Expired - Lifetime
- 2004-03-05 DE DE602004029882T patent/DE602004029882D1/en not_active Expired - Lifetime
- 2004-03-05 CN CNB2004800120347A patent/CN100379784C/en not_active Expired - Lifetime
- 2004-03-05 EP EP04718099A patent/EP1622958B1/en not_active Expired - Lifetime
- 2004-03-05 JP JP2006509189A patent/JP4764335B2/en not_active Expired - Lifetime
- 2004-03-05 CN CN200810003050XA patent/CN101195935B/en not_active Expired - Lifetime
-
2005
- 2005-11-04 KR KR1020057021027A patent/KR101092088B1/en active IP Right Grant
-
2008
- 2008-11-03 HK HK08112045.2A patent/HK1120296A1/en not_active IP Right Cessation
Patent Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3184426A (en) | 1959-04-17 | 1965-05-18 | Bayer Ag | Polyurethane elastic fibers and a method of producing the same |
US3557044A (en) | 1962-06-07 | 1971-01-19 | Du Pont | Process for making spandex polymers |
US3669934A (en) * | 1964-05-26 | 1972-06-13 | Celanese Corp | Improved elastomeric fibers |
US3475377A (en) | 1964-12-08 | 1969-10-28 | Bayer Ag | Spandex fibers based on segmented polyurethanes chain extended with two different chain extenders |
GB1102819A (en) | 1966-02-01 | 1968-02-14 | Du Pont | Segmented polyurethanes and process therefor |
US3631138A (en) | 1967-02-17 | 1971-12-28 | Timothy Victor Peters | Solution stable urethane polymer compositions and products therefrom |
US5000899A (en) | 1988-05-26 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Spandex fiber with copolymer soft segment |
US4973647A (en) | 1989-05-31 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Fiber from polyether-based spandex |
US5032664A (en) | 1989-10-03 | 1991-07-16 | Bayer Aktiengesellschaft | Process for the production of segmented polyurethane urea elastomer solutions and filaments and films thereof |
US5061426A (en) * | 1989-10-03 | 1991-10-29 | Bayer Aktiengesellschaft | Process for producing elastane fibers of high elasticity and strength |
JPH0782608A (en) | 1993-09-10 | 1995-03-28 | Asahi Chem Ind Co Ltd | Prodution of high-tenacity eleasic yarn |
US5539037A (en) | 1993-09-30 | 1996-07-23 | E. I. Du Pont De Nemours And Company | Spandex containing certain alkali metal salts |
JPH0820625A (en) | 1994-07-07 | 1996-01-23 | Mitsui Toatsu Chem Inc | Production of polyurethane urea solution |
JPH08176268A (en) | 1994-12-26 | 1996-07-09 | Mitsui Toatsu Chem Inc | Production of polyurethaneurea molding |
US5879799A (en) | 1995-06-23 | 1999-03-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Elastic polyurethane fibers and process for production thereof |
US5644015A (en) | 1996-07-24 | 1997-07-01 | Hyosung T & C Co., Ltd. | Process of manufacturing improved polyurethane fiber polymer |
US5843357A (en) | 1996-10-11 | 1998-12-01 | Arco Chemical Technology, L.P. | Spandex elastomers |
US5723563A (en) | 1996-10-11 | 1998-03-03 | Arco Chemical Technology, L.P. | Spandex elastomers |
US5948875A (en) | 1998-03-26 | 1999-09-07 | E. I. Du Pont De Nemours And Company | Polyurethaneureas and spandex made therefrom |
US5981686A (en) | 1998-03-26 | 1999-11-09 | E. I. Du Pont De Nemours And Company | Spandex made with 1,3-diaminopentane |
US6637181B1 (en) * | 1998-06-02 | 2003-10-28 | Bayer Aktiengesellschaft | Elastane threads and method for the production thereof |
US20020193550A1 (en) | 1999-12-03 | 2002-12-19 | Hiroshi Nishikawa | Spandex having low set at low temperatures |
US6639041B2 (en) * | 1999-12-03 | 2003-10-28 | Dupont-Toray Co. Ltd. | Spandex having low set at low temperatures |
US6472494B2 (en) | 2000-04-26 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Spandex with high heat-set efficiency |
WO2002086208A1 (en) | 2001-04-19 | 2002-10-31 | Kolon Industries, Inc | A polyurethane type elastic fiber, and a process of preparing for the same |
US20020161137A1 (en) * | 2001-04-30 | 2002-10-31 | Wilkinson W. Kenneth | Melt spun thermoplastic polyurethanes useful as textile fibers |
US6403682B1 (en) | 2001-06-28 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Spandex containing quaternary amine additives |
US6692828B2 (en) | 2002-04-29 | 2004-02-17 | Hyosung Corporation | High chlorine and heat resistant spandex fiber and manufacturing method thereof |
US6624281B1 (en) * | 2002-05-30 | 2003-09-23 | Bayer Corporation | Polyurethane/ureas useful for the production of spandex and a process for their production |
US20030225242A1 (en) * | 2002-05-30 | 2003-12-04 | Lawrey Bruce D. | Prepolymer catalysts suitable for preparing spandex fibers |
US20030224683A1 (en) * | 2002-05-30 | 2003-12-04 | Lawrey Bruce D. | Polyurethane/ureas useful for the production of spandex and a process for their production |
US6737497B2 (en) * | 2002-05-30 | 2004-05-18 | Bayer Polymers Llc | Polyurethane/ureas useful for the production of spandex and a process for their production |
US6720403B1 (en) * | 2002-11-01 | 2004-04-13 | E.I. Dupont De Nemours And Co. | Polyurethaneurea and spandex comprising same |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050165200A1 (en) * | 2003-05-05 | 2005-07-28 | Invista North America S.A.R.L. | Dyeable spandex |
US7838617B2 (en) * | 2003-05-05 | 2010-11-23 | Invista North America S.àr.l. | Dyeable spandex |
US20060270821A1 (en) * | 2005-05-09 | 2006-11-30 | Palmer Charles F Jr | Spandex compositions for high speed spinning |
US8765901B2 (en) | 2005-05-09 | 2014-07-01 | Invista North America S.ár.l. | Spandex compositions for high speed spinning |
CN104153037A (en) * | 2014-08-13 | 2014-11-19 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber with moisture absorption and moisture liberation performance |
CN106884332A (en) * | 2017-03-27 | 2017-06-23 | 浙江鸿辰新材料科技有限公司 | A kind of elastic polyurethane silk fiber and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP4764335B2 (en) | 2011-08-31 |
JP2006525410A (en) | 2006-11-09 |
DE602004029882D1 (en) | 2010-12-16 |
BRPI0409052B1 (en) | 2013-07-16 |
WO2004099282A1 (en) | 2004-11-18 |
ES2353758T3 (en) | 2011-03-04 |
ATE486897T1 (en) | 2010-11-15 |
CN101195935A (en) | 2008-06-11 |
CN100379784C (en) | 2008-04-09 |
KR101092088B1 (en) | 2011-12-12 |
BRPI0409052A (en) | 2006-03-28 |
CN1784443A (en) | 2006-06-07 |
EP1622958A1 (en) | 2006-02-08 |
KR20060012279A (en) | 2006-02-07 |
CN101195935B (en) | 2011-04-13 |
HK1120296A1 (en) | 2009-03-27 |
US20040225101A1 (en) | 2004-11-11 |
EP1622958B1 (en) | 2010-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6916896B2 (en) | High productivity spandex fiber process and product | |
US5000899A (en) | Spandex fiber with copolymer soft segment | |
US20050288477A1 (en) | Spandex of a particular composition and process for making same | |
US6472494B2 (en) | Spandex with high heat-set efficiency | |
US6503996B1 (en) | High-uniformity spandex and process for making spandex | |
EP1276786B1 (en) | Spandex with high heat-set efficiency | |
EP2524072B1 (en) | Spandex with high uniformity | |
KR101945493B1 (en) | spandex having cinstant molecular weight and manufacturing method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: E.I DU PONT DE NEMOURS AND COMPANY, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOUSER, NATHAN E.;SELLING, GORDON W.;REEL/FRAME:014390/0973;SIGNING DATES FROM 20031106 TO 20031110 |
|
AS | Assignment |
Owner name: INVISTA NORTH AMERICA S.A.R.L., DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:E. I. DU PONT DE NEMOURS AND COMPANY;REEL/FRAME:015286/0708 Effective date: 20040430 |
|
AS | Assignment |
Owner name: JPMORGAN CHASE BANK, N.A., TEXAS Free format text: SECURITY INTEREST;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L. F/K/A ARTEVA NORTH AMERICA S.A.R.;REEL/FRAME:015592/0824 Effective date: 20040430 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AG Free format text: SECURITY AGREEMENT;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L.;REEL/FRAME:022416/0849 Effective date: 20090206 Owner name: INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH Free format text: RELEASE OF U.S. PATENT SECURITY INTEREST;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT (F/K/A JPMORGAN CHASE BANK);REEL/FRAME:022427/0001 Effective date: 20090206 |
|
AS | Assignment |
Owner name: INVISTA NORTH AMERICA S.A.R.L., NORTH CAROLINA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:DEUTSCHE BANK AG NEW YORK BRANCH;REEL/FRAME:027211/0298 Effective date: 20111110 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: WILMINGTON TRUST (LONDON) LIMITED, AS SECURITY AGE Free format text: SECURITY INTEREST;ASSIGNOR:A&AT LLC;REEL/FRAME:048208/0120 Effective date: 20190131 Owner name: WILMINGTON TRUST (LONDON) LIMITED, AS SECURITY AGENT, GREAT BRITAIN Free format text: SECURITY INTEREST;ASSIGNOR:A&AT LLC;REEL/FRAME:048208/0120 Effective date: 20190131 |
|
AS | Assignment |
Owner name: A&AT LLC, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INVISTA NORTH AMERICA S.A R.L.;REEL/FRAME:050075/0645 Effective date: 20180101 |
|
AS | Assignment |
Owner name: THE LYCRA COMPANY LLC, DELAWARE Free format text: CHANGE OF NAME;ASSIGNOR:A&AT LLC;REEL/FRAME:050397/0397 Effective date: 20190517 |